Dyeing keratinous fibers with azaindoanilines

ABSTRACT

Hair dye and hair setting lotion compositions containing an indoaniline having the formula   WHEREIN R1, R2, R3 and R4 represent hydrogen, halogen, lower alkyl having one to four carbon atoms and lower alkoxy having one to four carbon atoms.

United States Patent 11 1 Kalopissis et al. 11 Oct. 1, 1974 [54] DYEING KERATINOUS FIBERS WITH 3,536,436 10/1970 Lange 8/10.2 Z N O LI 3,567,678 3/1971 Kalopissis 8/10.2 X

3,617,163 11/1971 Kalopissis et al. 8/10.1X [75] n ento s: G goi op Pans; Andree 3,712,790 1/1973 Kalopissis et al. 8/l0.2

Bugaut, Boulogne-sur-Seine; Francois Estradier, Paris, a f FOREIGN PATENTS OR APPLICATIONS France 1,025,414 4/1966 Great Britain 8/10.2 1 4 8 10.2 [73] Assignee: Societe Anonyme dite: LOreal, 1318972 2/ 96 France Pans France Primary Examiner-Stanley J. Friedman Filedi Ju y 1971 Assistant ExaminerVera C. Clarke NO 1 Attorney, 1482', or Firm-Cushman, Darby and 7 Cushman Related US. Application Data [63] Continuation-impart of Ser. No. 97,395, Dec. 11, g

1970, abandoned, which is a continuation-in-part of [57] ABSTRACT Ser. No, 45,564, June 11, I970, abandoned. Hair dye and hair setting lotion compositions contaming an indoaniline having the formula [30] Foreign Application Priority Data July 13, 1970 Luxembourg 61316 52 us. 131 8/10, 8/l0.1, 8/l0.2,

8/11, 8/79, 260/296 R, 424/DIG. 1, 424/DIG. 2, 424/49, 424/71 [51] Int. Cl D06p 3/04 [58] Field of Search 260/296 R; 8/l0.2, 10.1,

8/10, 11 wherein R R R and R represent hydrogen, ha1ogen, lower alkyl having one to four carbon atoms and [56] References Cited lower alkoxy having one to four carbon atoms.

UNITED STATES PATENTS 11 Claims, N0 Drawings 3,253,980 5/1966 Klinge et al 8/l0.2 X

DYEING KERATINOUS FIBERS WITH AZAINDOANILINES This application is a continuation-in-part of our application Ser. No. 97,395, filed Dec. 11, 1970, now abandoned, which, in turn, is a continuation-in-part of our application Ser. No. 45,564, filed June 11, 1970, now abandoned.

The present invention relates to a new dye composition for keratinous fibers, especially human hair and, more particularly, to a dye composition containing in solution at least one indoaniline having the formula:

wherein R R R and R each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl containing one to four carbon atoms and lower alkoxy containing from one to four carbon atoms, it being understood that these compounds can be present in a tautomeric form of that represented by formula I.

The dye compositions of the invention can be aqueous solutions, including aqueous solutions of a lower alkanol. Additionally, the aqueous solutions can include a cosmetic resin, especially when a colored hair setting lotion is contemplated.

The dye composition of the present invention contains from about 0.002-1 percent by weight, preferably between 0.0050.5 percent by weight of said indoaniline.

The indoaniline as defined above can be used alone, in which case it is possible to obtain on white hair shades rich in glints which range from parme to green, and in particular, very bright blues and silver grays. However, the indoanilines of this invention can also be used in admixture with other capillary dyes such as nitrobenzene, anthraquinone, oxazine and azine dyes. The composition of this invention can also include indophenols, indamines or other indoanilines.

The pH of the dye composition of the present invention can vary within wide limits, and generally the pH will range between 4 and l l, and preferably between 6 and 10.

As stated above, the dye composition of this invention can be in the form of an aqueous solution including an aqueous lower alkano] solution, but it can also contain conventionally employed cosmetic thickeners and thus take the form of creams or gels.

The dye composition of the present invention can additionally include various ingredients that are customarily used in cosmetics, such as wetting agents, dispersants, swelling agents, penetrating agents, emollients or perfumes, and it can also be packaged under pressure in aerosol cans or containers using conventional aerosol propellants such as the chlorofluorohydrocarbons including dichlorodifluoromethane, trichloromonofluoromethane and their mixtures.

The dye composition of the present invention is readily prepared by dissolving in water or in a mixture of water and a lower alkanol such as ethanol and isopropanol, one or more indoanilines as defined above, alone, or in admixture with another dye.

The dyeing of keratinic fibers, particularly human hair, by means of the dye composition of the invention can be effected in the usual way by applying the composition on the fibers that are to be dyed in amounts effective to color the fibers, permitting the composition to remain in contact with the fibers for about 5 to 30 minutes, rinsing the fibers and, if desired, washing the fibers, followed by drying the thus dyed fibers.

When the dye composition of the present invention is to be used as a hair setting lotion, the above defined indoaniline is present in amount generally ranging from about 0.002-0.5 percent by weight of the total composition.

10,000 to 700,000, copolymer of crotonic acid and vinyl acetate, copolymer of vinylpyrrolidone and vinyl acetate wherein the ratio of PVP to PVA range between 50-70: 50-30, copolymer of maleic anhydride and butylvinyl ether and the like.

The alcohols suitable for preparation of the hair setting lotions of this invention are lower alkanols, preferably ethanol and isopropanol, which are present in amounts of about 20-70 percent by weight of the total composition. The pH of the hair setting lotion generally ranges between about 5-8.

The hair setting lotions can contain as a coloring agent, only the indoanilines as defined above, if desired, in which case such compositions are termed shading compositions which impart to the hair or iibers bright colorings rich in pearly or iridescent glints. However, the hair setting lotion compositions can also contain other direct dyes such as those mentioned above.

These hair setting lotions are utilized in the customary way by applying the same to set wet hair which has been washed and rinsed, followed by rolling up on curlers and drying of the hair.

The indoanilines of this invention can be prepared according to two different processes. One method of producing the indoanilines comprises condensing 2,6- diamino pyridine on a paraaminophenol having the formula:

lka R4 wherein R R R and R, have the meanings given above, or on a salt of said paraaminophenol. This condensation reaction is effected in an aqueous alkaline medium having a pH ranging from about 9 to 12, in the presence of an oxidizing agent and at a temperature between 5 to 40C.

The pH of the reaction medium can be adjusted by the incorporation therein of a water soluble alkalinizing agent such as sodium hydroxide, potassium hydroxide and ammonia.

The oxidizing agent used in this condensation reaction can be, for example, hydrogen peroxide, a peroxy salt such as an alkaline persulfate including potassium persulfate and ammonium persulfate, and potassium ferricyanide. The oxidizing agent is generally present in amounts ranging from about 1 to 2 moles per mole of paraaminophenol.

The condensation reaction medium can also include an auxiliary solvent such as a lower alkanol or acetone, in which case the auxiliary solvent can be present in amounts ranging from about to 40 weight percent of the total weight of the solvents.

Representative paraaminophenols that can be used to prepare the indoanilines of the present invention include paraaminophenol, 2-methyl-4-amino phenol, 2,6-dimethyl-4-amino phenol, 3-methyl-4-amino phenol, 3,5-dimethyl-4-amino phenol, 2,3-dimethyl-4- amino phenol, 2-chloro-4-amino phenol and 3-chloro- 4-amino phenol.

Representative salts of the paraaminophenol that can be used include the hydrochloride, hydrobromide and sulfate thereof.

The mole ratio of 2,6-diaminopyridine to paraaminophenol can range between about 0.5/1 to 4/1 and is preferably about I/ 1.

A second process for producing the indoanilines of the present invention comprises condensing 2,6- diamino pyridine on a quinonechloroimide having the formula:

wherein R R R and R have the meaning given above. This condensation reaction is effected in an aqueous alkaline medium having pH ranging from about 8 to 1 1, and at a temperature between 5-40C.

The pH of the reaction medium can be adjusted by the incorporation therein of a water soluble alkalinizing such a sodium hydroxide, potassium hydroxide and ammonia.

The condensation reaction medium can also include an auxiliary solvent such as a lower alkanol or acetone, in which case the auxiliary solvent can be present in amounts ranging from about to 70 weight percent of the total weight of the solvents.

Representative quinonechloroimides that can be used to prepare the indoanilines of the present invention include quinonechloroimide, 2-methyl quinonechloroimide, 3-methyl quinonechloroimide, 2,6- dimethyl quinonechloroimide and 3-chloro quinonechloroimide.

The mole ratio of 2,6-diaminopyridine to quinonechloroimide defined above can range between about l/l to 0.5/1 and is preferably 1/1.

The following examples are intended to illustrate the different aspects of the present invention. The temperature indicated in these examples are expressed in degrees Centigrade and, unless otherwise specified, all parts and percentages are by weight.

EXAMPLE 1 N-[(2', 4'-diamino 3'-aza)phenyl] benzoquinone imine is prepared as follows.

Into 250 cc of water to which have been added 100 cc of ammonia at 22Be. there are dissolved 0.07 mole (7.7 g) of 2.6-diamino pyridine and 0.07 mole (7.6 g) of paraaminophenol. To this solution there is added,

- little by little, with stirring, 0.07 mole 15.96 g) of an monium persulfate in solution in 175 cc of water. When the addition is finished, the reaction mixture is left for 15 minutes. The resulting precipitate is filtered, washed with water and dried. 7.6 g of crude aza indoaniline are obtained which, after recrystallization in a dimethylformamide-water mixture, melts at 235C.

Preparation of N-[(2',4-diamino-3-aza)phenyl]-2- methyl benzoquinone imine.

0.1 mole (12.3 g) of 2-methyl-4-amino phenol is dissolved in 200 cc of 0.5 N soda. To this resulting solution, cooled in ice, there are added, first, 0.1 mole (22.8 g) of ammonium persulfate previously dissolved in cc of water to which is added 50 cc of ammonia at 22Be then, in a second stage, 0.1 mole (10.9 g) of 2,6-diamino pyridine in solution in cc of water. The resulting precipitate is then filtered, washed with water and dried under a vacuum. 9.14 g of the desired indoaniline, chromatographically pure and which melts at 132 are recovered.

Preparation of N-l(2',4'-diamino-3'-aza)phenyl]- 2,6-dimethyl benzoquinone imine.

0.1 mole (10.9g) of 2,6-diamino pyridine is dissolved in 125 cc of water, to which are added 100 cc of ammonia at 22Be. To this resulting solution, cooled in ice, there are added, little by little, with stirring and simultaneously, with the aid of two dropping funnels, on the one hand, 0.025 mole (4.8 g) of monohydrochloride, monohydrate of 2,6-dimethyl-4-amino phenol in solution in 100 cc of water, and on the other hand, 0.025 mole (5.7 g) of ammonium persulate in solution in 20 cc of water. The resulting precipitate obtained is filtered, washed with water and dried. Thus 3 g of crude indoaniline are obtained whose chromatogram reveals the presence of about 10 percent of a secondary product. When the impure indoaniline is dissolved in a minimum of ethyl alcohol at 25, cooled to 0 and, little by little, water is added to the alcohol solution, essentially all of the secondary product is precipitated in the form of mordore crystals. This product is chromatographi- Analysis Calculated for C l- 19 Found EXAMPLE 4 Preparation of N-[(2,4-diamino-3-aza)phenyl]-5- methyl benzoquinone imine.

0.06 mole (6.5 g) of 2,6-diamino pyridine is dissolved in 50 cc of water to which is added 25 cc of ammonia at 22Be. To this resulting solution, cooled in ice, are added, little by little, with stirring and simultaneously, with two dropping funnels, on the one hand, 0.04 mole (9.12 g) of ammonium persulfate in solution in 50 cc of water, and, on the other hand, 0.04 mole (8.16 g) of 3-methyl-4-amino phenol hydrobromide in solution in 25 cc of water. The resulting precipitate obtained is filtered, washed with water and dried. Thus 4.2 g of the desired indoaniline are obtained which, after recrystallization in a dimethylformamide-water mixture, melts with decomposition at 142.

Preparation of N-[(2,4'-diamino-3'-aza) phenyl]-5- chloro benzoquinone imine.

0.036 mole (3.9 g) of 2,6-cliamino pyridine is dissolved in 30 cc of water to which are added cc of ammonia at 22Be. To this resulting solution, cooled in ice, there are added, little by little, with stirring and simultaneously, with the aid of two dropping funnels, on the one hand, 0.03 mole (6.84 g) of ammonium persulfate in solution in 25 cc of water, and, on the other hand, 0.03 mole (5.4 g) of 3-chloro-4-amino phenol hydrochloride in solution in 50 cc of water. The resulting precipitate obtained is filtered, washed with water and dried. Thus, 3.6 g of the desired indoaniline are obtained in the form of mordore green crystals. After recrystallization in a dimethylformamide-water mixture, the product melts with decomposition at 248.

Molecular mass calculated for C H CIMO Molecular mass found by potentio- 5 metric determination in acetic acid by perchloric acid Analysis Calculated for C,,H,,ClN,O Found C72 3 H7: 3 N7: 2

LAN-

EXAMPLE 6 Preparation of N-[(2',4' diamlino-3'-aza) phenyl]- 2,5-dimethyl benzoquinone imine having the formula:

Initially, 0.02 mole (2.74 g) of 2,5-dimethyl-4-amino Molecular mass calculated for C H N O, 0.5 H 0 Molecular mass found by potentiometric determination in acetic acid by perchloric acid Calculated Analysis for C H N O 0.5 H 0 Found EXAMPLE 7 Preparation of N-[(2',4-diamino-3'-aza) phenyll 2- chloro benzoquinone imine.

The supernatant liquid is centrifuged, decanted and the precipitate is washed three times in ice water by successive centrifugings and decantings. After drying under vacuum, the product obtained (2.7 g) is chromatographically pure and melts at 250.

Preparation of N-[(2',4-diamino-3'-aza) phenyl]- 2,3-dimethyl benzoquinone imine having the formula:

N H2 CH CH3 0.02 mole (2.74 g) of 2,3-dimethyl-4-amino phenol is dissolved in 30 cc of a normal soda solution. Then 0.02 mole (2.18 g) of 2,6-diamino pyridine is dissolved in 100 cc of water. The two solutions thus prepared are mixed. After the mixture is cooled to C there is then added 0.02 mole (4.56 g) of ammonium persulfate in solution in 50 cc of water to which are added 20 cc of ammonia at 22Be. The reaction mixture is left for 20 minutes at 0. The desired azaindoaniline, crystallized in the form of green crystals with golden glints (2.3 g), is filtered. After recrystallization in a dimethylformamide-water mixture, the product is chromatographically suitable and metls at 242.

Analysis Calculated for C,,,H N..O Found C71 64.46 64.76 64.2] H71 5.78 5.88 5.82 N7z 23.14 23.22 23.11

EXAMPLE 9 Preparation of N-[(2,4-diamino-3'-aza) phenyl]- 3,5-dimethyl benzoquinone imine.

under a vacuum. The product is chromatographically pure and melts at 211.

Molecular mass calculated for C H MO 242 Molecular mass found by potentiometric determination in methylisobutylkctone hy perchloric acid 245 EXAMPLE 10 Preparation of N-[(2,4-diamino-3'-aza) phenyl]-5- methyl benzoquinone imine having the formula:

0.01 mole (1.55 g) of 3-methyl quinonechloroimide is dissolved in 30 cc of ethyl alcohol. Then 0.01 mole (1.09 g) of 2,6-diamino pyridine is dissolved in 10 cc of water to which have been added 10 cc of ammonia at 20Be and 1 cc of normal soda solution. The two solutions, previously cooled, are mixed and the reaction mixture isleft for an hour at ambient temperature. 50 cc of ice water are added and 0.85 g of the desired indoaniline precipitate and are filtered which after washing with water and ethyl alcohol and drying under a vacuum, melt at 144 (no lowering of the melting point used in mixture 'with the product of example 4).

Molecular mass calculated for C,. .H N..O Molecular mass found by potentiometric determination in acetic acid by perchloric acid EXAMPLE 1 1 Preparation of N-[(2,4 diamino-3-aza) phenyl]-5- chlorobenzoquinone imine having the formula:

0.01 mole (1.76 g) of 3-chloro quinonechloroimide is dissolved in 30 cc of ethyl alcohol. Then 0.01 mole (1.09 g) of 2,6-diamino pyridine is dissolved in 10 cc of water to which are added 10 cc of ammonia at 22Be 0 and 1 cc of normal soda solution. The resulting two previously cooled solutions are mixed and this reaction mixture is left for 20 minutes at ambient temperature. The desired indoaniline (1.5 g) precipitates and is filtered, washed with water then with acetone and, after drying under a vacuum, it melts at 246 (no lowering of the melting point used in mixture with the product of example 5).

2 Molecular mass calculated for C H Cl N 2485 The indoaniline of Example 2 0.4 Molecular mass found by potentiometric Crotonic acid-vinyl acetate copolymer determination in acetic acid by per- 5 (%]9072 molecular weight 45,000) 2 chloric acid 252 96 ethyl alcohol 50 Triethanolamine, sufficient for pH 7 Water, sufficient for 100 EXAMPLE 12 This hair setting lotion is applied to brown hair and i .r The followmg ha dye composltlon ls prepared: 10 imparts thereto a brownish black coloring with l rides cent gllnts.

EXAMPLE 17 g The indoaniline of Examlvle 2 The followin hair settin lotion is re ared: 96 ethyl alcohol 20 g g p p Ammonia in 22Be sufficient for pH 10 Water, sufficient for 100 g The indoaniline of Exam le 2 0.0l 5 This hair dye composit on, when applied to 95 per- N44l hydrox'y)pheqyi].famimmmeihyl cent naturally white hair for minutes, imparts C t l q I ro onlc aci -viny aceta e copo ymer thereto, after rinsing and shampooing, a blue green col- 2O 10% mm molecular weight 48mm Ol'lIlg. 96 ethyl alcohol 50 Triethanolamine, sufficient for pH 7 EXAMPLE 13 Water sufficient for 100 The following hair dye composition is Prepared1 This hair setting lotion is applied to 100 percent 25 white bleached hair and imparts thereto a dark golden blond coloring.

g The indoaniline of Example 2 0.! 96 ethyl alcohol 20 EXAMPLE l3 1% lactic acid solution sufficient for pH 5 ware, sumciem f 100 The following hair dye composition is prepared:

This hair dye composition, when applied to 95 pern g cent naturally I white hair for 20 minutes, imparts The indoanmne Example 2 (m5 thereto, after rinsing and shampooing, a clear silvery Nitroparaphenylenediamine 0.2

' 96 ethyl alcohol 50 turquolse Colormg Ammonia at 22Be, sufficient for pH 8i EXAMPLE 1 Water, sufficient for 100 The following hair dye composition is prepared: The hair dye composition is applied to 60 percent naturally white hair and imparts thereto a dark brown coloring with copper glints.

g 40 The indoaniline of Example 2 0.05 EXAMPLE 19 Butylglycol 5 Lauryl alcohol oxyethylenated with I 05 mom of ethylene oxide 5 The following hair setting lotion is prepared. Water, sufficient for 100 g This hair dye composition, wh ch has a pH of 7 is apv The indoanmn? of Example 2 M4 plied to 95 percent naturally white hair for 20 minutes. -l(2',4' amlno 5'-me; hgxy)phen =ll o I enzoquinone imlne If] y rate After rinsing and shampooing, a pearly bluish clear Cromnic acidwiny] acetate polymer green coloring 15 obtained. (love/90% molecular weight 50,000 2 96 ethyl alcohol EXAMPLE 15 5O Triethanolamine, sufficient for pH 7 Water sufficient for 100 The following hair setting lotion is prepared:

This hair setting lotion is applied to 100% white bleached hair and imparts thereto a clear brown-purple g The indoanilinc of Example 2 0.2 Shade wlth pearly glmts' Crotoliic acid-vinyl acetate copolymer (l0lc/9071 molecular weight 45,000) 2 EXAMPLE 20 96 eth 1 alcohol 50 rriciimi i s m fo pH 7 The following hair setting lotion is prepared: Water, sufficient for 100 This hair setting lotion, applied to 100 percent white The V d T e of E m k 3 g l In in X3 bleached hair, imparts thereto an intense ultramarine ggg acetaite copolymer coloring. When applied to percent naturally white yogi/90% molecular weight 50,000) 2 hair, it imparts thereto an ultramarine coloring with sil- 2.2;; Sumciem for PH 7 50 very gllIltS. 65 Water, sufficient for EXAMPLE 16 This hair setting lotion is applied to 100 percent The following hair setting lotion is prepared: white bleached hair and imparts thereto a very brilliant 1 1 1 2 intense pure blue shade. This same solution is then aplied to 95 ercent naturall white hair and imparts This hair d e com osition is a lied to 95 ercent P P y y P PP P thereto a pure blue shade wlth silvery gllnts. naturally whlte halr for 25 mlnutes and lmparts thereto sil ra. colorin with sli ht mauve lints. EXAMPLE 21 5 a very g y g g g The following hair setting lotion is prepared: EXAMPLE 26 The following hair setting lotion is prepared:

' g The indoaniline of Example 3 0.03 N-[(3',5-dimethyl-4'hydroxy)phenyl]-2,6- l0 g dimethyl benzoquinone imine 0.1 The l l P ExamPle l (H Crotonic acid-vinyl acetate copolymer C t nlc a ld-vlnyl ac tate copolymer lO%/90% molecular weight 48.000) 2 molecular'weight 45.0 3 96 ethyl alcohol 50 96 ethyl alcohol 50 Triethanolamine. sufficient for pH 7 Triethanolamine, sufficient for pH 7 Water, sufficient for I00 Water, sufficient for 100 This hair setting lotion is applied to 100 perc nt This hair setting lotion is applied to 100 percent whlte bleached halt an imp rts e e a mauve C0l0rwhite bleached hair and imparts thereto an iridescent parme coloring. This same hair setting lotion is also ap- EXAMPLE 22 plled to 95 percent naturally whlte hair and imparts thereto a slate blue colorlng. The following hair dye composltlon 15 prepared:

EXAMPLE 27 g The following hair setting lotion is prepared: The indoaniline of Example 3 0.] 96 ethyl alcohol 20 Ammonia at 22Be, sufficient for pH 10 g The lndnflnlllne of Example 4 0.l

Crotonic acid-vinyl acetate copolymer This hair dye composition is applied to 95 percent 960 L T "fi '8 naturally white hair for 10 minutes and imparts thereto, 30 f i l m Sufficient for pH 7 after rinsing and shampooing, a Cyprian green color Water, sufficient for 100 ation.

This hair settin lotion is a lied to 100 ercent EXAMPLE 23 PP p whlte bleached halr and lmparts thereto a brlght blue The following hair dye composition is prepared: shade with parme glints. This same hair setting lotion is also applied to 95 percent naturally white hair and imparts thereto a myosotis blue shade with silvery g The indoaniline of Example 3 0.1 glmts' 96 ethyl alcohol 20 1'71 lactic acid solution in water 40 EXAMPLE 28 sufficient for pH 5 Water. sufficlcnl for 100 The followlng halr dye composition is prepared:

This hair dye composition is applied to 95 percent naturally white hair for 15 minutes and imparts thereto, 32f g q l Example 4 s after rinsing and shampooing, a clear Cyprian green zgg gf g Sumcicm for pH 10 0g coloring. Water, sufficient for 100 cc EXAMPLE 24 This hair dye composition is applied to 95 percent The following hair dye composition is prepared: naturally white hair for 20 minutes, and imparts thereto, after rinsing and shampooing, a strongly silvered clear blue coloring.

g The indoaniline of Example I 0.25 96 isopropyl alcohol 20 I EXAMPLE 29 l lr22l3- lr' If H 10.5 'f,$;f"; g a, or p 100 The followlng halr setting lotlon ls prepared:

This hair dye composition is applied to 95 percent g naturally whlte halr for 25 mlnutes and imparts thereto The indouniline of Example 5 0'] 21 clear green blLllSh COlOI'll'lg. Crotonic acid-vinyl acetate copolymer (l0%/90% molecular weight 50,000) 2 EXAMPLE 25 96 ethyl alcohol 50 Triethanolamine, sufficient for pH 7 The following hair dye composition 18 prepared: Water. sufficient for 100 This hair setting lotion is applied to 100 percent g The indouniline of Example I 01 white bleached halrand mparts thereto a clear parme 96 lethyl alcohol 20 shade. This same hair setting lotion 18 also applied to 1% actic acid solution in water sufmm for PH 5 percent naturally whlte ban and lmparts thereto a 811- Water. sufficient for 100 very blue gray shade.

EXAMPLE 30 This hair setting lotion is applied to 100 percent The following hair dye composition is prepared: white bleached hair and imparts thereto an ash gray shade with slight mauve glints. g EXAMPLE 35 The indoaniline of Example 6 0.25 96 ethyl alcohol 25 The followlng hair setting lotion is prepared: Water, sufficient for I00 Ammonia, at 22Be sufficient for pH g The hair dye composition is applied to 95 percent 10 The i oa ne of xa ple 8 0 005 naturally white hair for minutes at ambient tempera- 3 2 ture and imparts thereto, after rinsing and shampooing, 96 ethyl alcohol, sufficient for 50 a strongly pearly clear turquoise blue coloring.

Triethanolamine, sufficient for pH 7 EXAMPLE 3 1 l5 T'h' tt' lt' l'dtlOO t The following hair setting lotion is prepared: hls a" Se mg 01cm ls apple 0 percen white bleached hair and imparts thereto a pearly appearance with slight green glints.

g Dye of Example 6 0.10 2() EXAMPLE 36 Copolymer of 10% crotonic acid 90% Vinyl acetate (molecular weight The following hair dye composition is prepared. 45,000 50.000) 2 96 ethyl alcohol 50 Water, sufficient for 100 g Triethanolamine, sufficient for pH 7 The indoaniline of Example 8 0.1

96 ethyl alcohol t r 100 This hair setting lotion is applied to 100 percent 3? 22, 32 equal to 7 white bleached hair and imparts thereto a strongly sil- Vered myosotls blue Shade- This hair dye composition is applied to 95 percent EXAMPLE 32 30 naturallywhlte hair for 20 mmutesat ambient temperature and imparts thereto, after rmslng and shampoomg, The following hair dye composition is prepared: a il bl gray l i EXAMPLE 37 The indoaniline of Example 6 3 The following hair setting lotion is prepared: 96 ethyl alcohol 20 Water. sufficient for 100 10% lactic acid in water, sufficient g PH The indoaniline of Example 9 0.05

Vinyl acetate-crotonic acid copolymer This hair dye composition is applied to 95 percent s g g fg naturally white hair for 20 minutes at ambient tempera- 40 water, Sumciem fo 100 ture and imparts thereto, after rinsing and shampooing, Triethanolaminev Sufficient for P 7 a silvery blue gray coloration.

This hair setting lotion 15 applied to 100 percent EXAMPLE 33 white bleached hair and imparts thereto a silver gray The following hair setting lotion is prepared: Shade Wlth Slight blue glmts- EXAMPLE 38 g The following hair dye composition is prepared: The indoaniline of Example 7 0.05 Vinyl acetate crotonic acid copolymer (as in Example 31) 2 96 ethyl alcohol 50 g Water, sufficient for 100 The indoaniline of Example 9 0.05 Triethanolamine, sufficient for pH 7 96 ethyl alcohol 30 Water. sufficient for 100 Ammonia, at 22Be sufficient for H 10 This hair setting lotion is applied to 100 percent p white bleached hair and imparts thereto a very bright This hair dye composition is applied to 95 percent emerald green Shadenaturally white hair for 10 minutes at ambient tempera- EXAMPLE 3 4 ture and imparts thereto, after rinsing and shampooing, a silver gray shade with green glints. The following hair setting lotion is prepared: w is claimed is:

l. A dye composition for keratinous fibers comprising an aqueous solution of an indoaniline of the forg The indoaniline of Example 7 0.025 mula N-l(3,5'-dimethyl-4'-hydroxy)phenyl]-2,

6dimethyl benzoquinone imine 0.05

Vinyl acetate-crotonic acid copolymer (of Example 31) 2 96 ethyl alcohol 50 Water, sufficient for 100 Triethanolamine, sufficient for pH 7 wherein R R R and Rgeach independently repre sent a member selected from the group consisting of hydrogen, halogen and lower alkyl having one to four carbon atoms, and the tautomeric forms thereof. said indoaniline being present in amounts of about 0.002 to 1 percent by weight of said composition.

2. The dye composition of claim 1, having a pH between 4 and 11.

3. The composition of claim 1 which also includes a nitrobenzene dye.

4. The composition of claim 1 which also includes a member selected from the group consisting of indophenol and a different indoaniline.

5. A hair setting lotion composition comprising a solution of an indoaniline of the formula 6. The hair setting lotion composition of claim 5, wherein said lower alkanol is selected from the group consisting ethanol and isopropanol.

7. The hair setting lotion composition of claim 5 wherein said cosmetic film forming resin is selected from the group consisting of polyvinylpyrrolidone having a molecular weight of about 10,000 to 700,000 and a copolymer of crotonic acid-vinyl acetate, 10/90 percent, having a molecular weight of 45,00050,000.

8. The hair setting lotion composition of claim 5 which also includes a nitro benzene dye.

9. The hair setting lotion composition of claim 5 which also includes a member selected from the group consisting of indophenol and a different indoaniline.

10. A process for dyeing human hair comprising impregnating the hair with the dye composition of claim 1 in amounts effective to color said hair, permitting said composition to remain in contact with said hair for a period of time ranging from about 5 to 30 minutes, rinsing said hair with water and drying said hair.

11. A method of setting and dyeing human hair comprising impregnating wet hair with the hair setting lotion of claim 5 in amounts effective to color and set said hair and then rolling up and drying said hair. 

1. A DYE COMPOSITION FOR KERATINOUS FIBERS COMPRISING AN AQUEOUS SOLUTION OF AN INDOANILINE OF THE FORMULA
 2. The dye composition of claim 1, having a pH between 4 and
 11. 3. The composition of claim 1 which also includes a nitrobenzene dye.
 4. The composition of claim 1 which also includes a member selected from the group consisting of indophenol and a different indoaniline.
 5. A hair setting lotion composition comprising a solution of an indoaniline of the formula
 6. The hair setting lotion composition of claim 5, wherein said lower alkanol is selected from the group consisting ethanol and isopropanol.
 7. The hair setting lotion composition of claim 5 wherein said cosmetic film forming resin is selected from the group consisting of polyvinylpyrrolidone having a molecular weight of about 10,000 to 700,000 and a copolymer of crotonic acid-vinyl acetate, 10/90 percent, having a molecular weight of 45,000-50,000.
 8. The hair setting lotion composition of claim 5 which also includes a nitro benzene dye.
 9. The hair setting lotion composition of claim 5 which also includes a member selected from the group consisting of indophenol and a different indoaniline.
 10. A process for dyeing human hair comprising impregnating the hair with the dye composition of claim 1 in amounts effective to color said hair, permitting said composition to remain in contact with said hair for a period of time ranging from about 5 to 30 minutes, rinsing said hair with water and drying said hair.
 11. A method of setting and dyeing human hair comprising impregnating wet hair with the hair setting lotion of claim 5 in amounts effective to color and set said hair and then rolling up and drying said hair. 